CN103545476A - PVDF-HFP (Polyvinylidene Fluoride-Hexafluoropropylene) microporous polymer membrane with anchoring and enhancing effects and preparation method thereof - Google Patents
PVDF-HFP (Polyvinylidene Fluoride-Hexafluoropropylene) microporous polymer membrane with anchoring and enhancing effects and preparation method thereof Download PDFInfo
- Publication number
- CN103545476A CN103545476A CN201310524062.8A CN201310524062A CN103545476A CN 103545476 A CN103545476 A CN 103545476A CN 201310524062 A CN201310524062 A CN 201310524062A CN 103545476 A CN103545476 A CN 103545476A
- Authority
- CN
- China
- Prior art keywords
- hfp
- pvdf
- polymer
- preparation
- grappling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a PVDF-HFP (Polyvinylidene Fluoride-Hexafluoropropylene) microporous polymer membrane with high liquid absorption rate, heat resistance and anchoring and enhancing effects and a preparation method thereof. The preparation method comprises the following steps: (1) dissolving PVDF-HFP in an organic solvent, heating and intensely stirring, adding cage type silsesquioxane after fully dissolving PVDF-HFP, and continuously heating and stirring for a period of time to obtain a colloid emulsion with better dispersibility; (2) uniformly mixing and stirring metal salt and a non-solvent; (3) dropwise adding the mixed liquid obtained by the step (2) into the colloid mixed liquid obtained by the step (1), and uniformly stirring; (4) casting the colloid mixed liquid obtained by the step (3) on a glass plate, and coating and forming the membrane. The preparation method is simple in process and applicable to laboratories and industrialized production as well as preparation of membranes for batteries and supercapacitors, and the preparation method can be further applied to thin film apparatuses based on piezoelectric property.
Description
Technical field
The present invention relates to a kind of PVDF-HFP micropore polymer diaphragm and preparation method with grappling humidification, belong to battery, electric capacity field.
Background technology
Along with the popularization gradually of new-energy automobile, future can be day by day ardent to the demand of lithium ion battery material.Barrier film, as the critical component of power lithium-ion battery, will directly affect capacity, cycle performance and the security performance of battery.In recent years, porous polymeric objects system has caused people's extensive concern, U.S. Bellcore in 1994 for company Kynoar-hexafluoropropylene (PVDF-HFP) by plasticising/extraction process, make the polymer film of microcellular structure, increased the pick up of polymer dielectric, but the shortcoming such as PVDF-HFP based polyalcohol barrier film exists that transference number of ions is low, thermal stability is bad and interface compatibility is bad.Research shows, adds inorganic matter in polymer dielectric, can improve the performance of polymer dielectric.
Patent CN102071487A discloses a kind of preparation method of organic-inorganic nano composite membrane, after soon raw material cellulose acetate and oligomeric polyhedral silsesquioxane are drifted along or through, by electrostatic spinning, prepares barrier film.But quiet spinning technique can not guarantee barrier film and have uniform porosity, inhomogeneous porosity, under the discharge scenario of large multiplying power, can cause heat-resisting inhomogeneous of battery, thereby affects the life-span of battery.
Patent CN102731944A discloses the preparation of a kind of sylvite/Kynoar-hexafluoropropylene copolymer composite membrane.Be about to after raw material silicon dioxide and Kynoar-hexafluoropropylene copolymer blended, casting film-forming on smooth glass plate, put it into oven drying 10h～20h, finally in Muffle furnace through heat treatment 0.5 h～8h, obtain Kynoar-hexafluoropropylene copolymer, sylvite composite membrane.The standby barrier film of this legal system has good conductivity, but this preparation technology is loaded down with trivial details, time-consuming.The mentality of designing of this patent is, adds inorganic matter in polymer dielectric, and " the grappling effect " by inorganic matter, is deposited in polymer dielectric in the interface of electrode, improves the mechanical strength under its liquid electrolyte existence.Ball cagelike silsesquioxane has good mechanical performance and hot property, is a kind of fabulous interpolation material.
Summary of the invention
The object of the present invention is to provide a kind of PVDF-HFP micropore polymer diaphragm with grappling humidification, it has good thermal stability, good mechanical strength and good imbibition/liquid-keeping property, the ionic conductivity of the lithium ion battery of assembling with this barrier film, cycle performance and security performance have had raising by a relatively large margin.
Another object of the present invention is to provide a kind of preparation method with the PVDF-HFP micropore polymer diaphragm of grappling humidification, and its technique is reasonable, easy, easily row and environmental protection.
For achieving the above object, technical scheme of the present invention is achieved in that the PVDF-HFP micropore polymer diaphragm with grappling humidification, it is characterized in that: hygrometric state barrier film component contains polymer P VDF-HFP, ball cagelike silsesquioxane, slaine, organic solvent and non-solvent, wherein each constituent mass proportioning of hygrometric state barrier film is: 5.2～17.4 parts of polymer P VDF-HFP10～14.5 part, 0.5～4.3 part of ball cagelike silsesquioxane, 0.05～0.6 part of slaine, 52.0～110 parts of organic solvents and non-solvents.
Described slaine is a kind of in calgon, potassium chloride, potash or two kinds.
Described organic solvent is acetone, DMF, one or both in 1-METHYLPYRROLIDONE.
Described non-solvent is a kind of in water, absolute ethyl alcohol.
The preparation method with the PVDF-HFP micropore polymer diaphragm of grappling humidification, it is characterized in that concrete steps are as follows: (1) is dissolved in polymer P VDF-HFP in organic solvent, through heating, stirring, treat that it fully dissolves, add goal cagelike silsesquioxane, continue strong heating, heating reflux temperature is 50 ℃～100 ℃; Stir after 2h～5h, obtain dispersed better colloid emulsion; (2) slaine and non-solvent are mixed, make mixed liquor standby; (3) mixed liquor obtaining in step (2) is dropwise added in the colloid emulsion being obtained by step (1), stir evenly; (4) adopt liquid the tape casting that the colloid mixed liquor in step (3) is cast on glass plate, blade coating film forming; Take off film, thickness is 18 μ m～45 μ m, at the temperature of 50 ℃～70 ℃, film is carried out to 1h～2h vacuum drying; Porosity is 30%～70%.
Described polymer P VDF-HFP weight average molecular weight is 400,000～500,000.
The mass ratio of described organic solvent and polymer P VDF-HFP is 5.3～7.6:1.
Good effect of the present invention: by raw material PVDF-HFP, ball cagelike silsesquioxane, slaine blend and in conjunction with boring technique, prepared barrier film has compared with high-liquid absorbing rate, mechanical strength and thermal endurance, cycle performance and the security performance of the lithium ion battery integral body being assembled into this barrier film improve greatly, and its preparation method is easy, easily row and environmental protection.
Accompanying drawing explanation
Fig. 1 obtains the photo of barrier film and the contrast of certain commercialization barrier film wettability with example 1 of the present invention.
Fig. 2 obtains diaphragm electrochemical stability window photo in example 3 of the present invention.
Fig. 3 is that example 4 of the present invention obtains barrier film and certain commercialization barrier film thermogravimetric curve picture.
Fig. 4 is the transference number of ions that the barrier film assembled battery with example of the present invention 5 preparations records.
Fig. 5 is that example 6 of the present invention respectively heats the photo of 1h with certain commercialization barrier film under 135 ℃, 165 ℃, 200 ℃ environment.
Fig. 6 is the SEM figure of embodiment 7.
Embodiment
In following concrete example is described, a large amount of concrete details have been provided so that more deep understand the present invention.Yet, it will be apparent to one skilled in the art that the present invention can be implemented without one or more these details.
embodiment 1
(1) 2.5g PVDF-HFP and 0.125g ball cagelike silsesquioxane are dissolved in 13.2g acetone; (2) 0.1 calgon and 1.32g absolute ethyl alcohol are mixed, dropwise add in step (1), continue stirring and obtain colloid mixed liquor; (3) the colloid mixed liquor being obtained by step (1), step (2) is cast on glass plate to blade coating film forming; (4) take off film, at the temperature of 50 ℃, film is carried out to 2h vacuum drying.The membrane thicknesses that this embodiment prepares of take is 18um, and porosity is 30%.Fig. 1 obtains with example of the present invention the photo that barrier film infiltrates 24h front and back, and barrier film prepared by application the present embodiment has good pick up, and pick up is high by 350%.
embodiment 2
(1) 2.5g PVDF-HFP and 0.75g ball cagelike silsesquioxane are dissolved in 19.0g acetone; (2) 0.0125 potassium chloride and 3.0g absolute ethyl alcohol are mixed, dropwise add in step (1), continue stirring and obtain colloid mixed liquor; (3) the colloid mixed liquor being obtained by step (1), step (2) is cast on glass plate to blade coating film forming; (4) take off film, at the temperature of 70 ℃, film is carried out to 1h vacuum drying.The membrane thicknesses that this embodiment prepares of take is 45um, and porosity is 70%.
embodiment 3
(1) 2.5g PVDF-HFP and 0.5g ball cagelike silsesquioxane are dissolved in 6g acetone and 12g 1-METHYLPYRROLIDONE; (2) mixture of 0.05 potassium chloride and 0.05 potash is dissolved in 2.0g water, dropwise adds in step (1), continue stirring and obtain colloid mixed liquor; (3) the colloid mixed liquor being obtained by step (1), step (2) is cast on glass plate to blade coating film forming; (4) take off film, at the temperature of 60 ℃, film is carried out to 2h vacuum drying.Fig. 2 is the electrochemical stability window picture that the embodiment of the present invention 2 obtains barrier film, as can be seen from the figure from open circuit voltage until 4.7V, electric current is very steady, until there is a small size electric current after surpassing 4.7 V, when electrode potential is greater than 5.0 V, respective electrical lumen is aobvious to be increased considerably, and this explanation polymer dielectric starts to occur electrochemical reaction.Hence one can see that, and the electrolyte of the type is at least electrochemical stability below 5.0 V.
embodiment 4
(1) 2.5g PVDF-HFP and 0.25g ball cagelike silsesquioxane are dissolved in 18g 1-METHYLPYRROLIDONE; (2) 0.0125g potash is dissolved in 1.8g water, dropwise adds in step (1), continue stirring and obtain colloid mixed liquor; (3) the colloid mixed liquor being obtained by step (1), step (2) is cast on glass plate to blade coating film forming; (4) take off film, at the temperature of 70 ℃, film is carried out to 2h vacuum drying.Fig. 3 is that example 4 of the present invention obtains thermogravimetric curve picture with certain commercialization barrier film.
embodiment 5
(1) PVDF-HFP that is 400,000 by 10.0g molecular weight is dissolved in 53.0g acetone, under 50 ℃ of backflows, strong stirring condition, treats that it fully dissolves and adds 0.5g ball cagelike silsesquioxane, and strong stirring, after a period of time, obtains dispersed better colloid emulsion; (2) 0.5g calgon is dissolved in 5.28g absolute ethyl alcohol; (3) mixed liquor obtaining in step 2 is dropwise added in the colloid mixed liquor being obtained by step 1, stir evenly; (4) the colloid mixed liquor in step 3 is cast on glass plate to blade coating film forming.The micro-pore diameter 20 μ m of the barrier film of preparing with this embodiment, transference number of ions testing time-curent change curve that transference number of ions is this embodiment up to 0.89, Fig. 4.
embodiment 6
(1) PVDF-HFP that is 500,000 by 10.0g molecular weight is dissolved in 76g N, in dinethylformamide, under 100 ℃ of backflows, strong stirring condition, treat that it fully dissolves and add 3g ball cagelike silsesquioxane, strong stirring, after a period of time, obtains dispersed better colloid emulsion; (2) mixture of 0.05g potassium chloride and 0.05g potash is dissolved in 12.0g water; (3) mixed liquor obtaining in step 2 is dropwise added in the colloid mixed liquor being obtained by step 1, stir evenly; (4) the colloid mixed liquor in step 3 is cast on glass plate to blade coating film forming.The good heat resistance of the barrier film of preparing with this embodiment, at 200 ℃, under 1h condition, to be only 1%, Fig. 5 respectively heat respectively the picture of 1h for this embodiment and certain commercialization barrier film under 135 ℃, 165 ℃, 200 ℃ environment in thermal contraction.
embodiment 7
(1) by 10.0g molecular weight, be that 45.5 ten thousand PVDF-HFP is dissolved in 24g acetone and 48g 1-METHYLPYRROLIDONE mixed solvent, under 70 ℃ of backflows, strong stirring condition, treating that it fully dissolves adds 1.0g ball cagelike silsesquioxane, strong stirring, after a period of time, obtains dispersed better colloid emulsion; (2) 0.4g potassium chloride is dissolved in 8.0g water; (3) mixed liquor obtaining in step 2 is dropwise added in the colloid mixed liquor being obtained by step 1, stir evenly; (4) the colloid mixed liquor in step 3 is cast on glass plate to blade coating film forming.The barrier film porosity of preparing with this embodiment is high, the SEM figure that Fig. 6 is this embodiment.
embodiment 8
(1) by 10.0g molecular weight, be that 45.5 ten thousand PVDF-HFP is dissolved in 72gN-crassitude ketone solvent, under 100 ℃ of backflows, strong stirring condition, treating that it fully dissolves adds 2.0g ball cagelike silsesquioxane, stirs after a period of time, obtains dispersed better colloid emulsion; (2) 0.1g potash is dissolved in 7.2g ethanol; (3) mixed liquor obtaining in step 2 is dropwise added in the colloid mixed liquor being obtained by step 1, stir evenly; (4) the colloid mixed liquor in step 3 is cast on glass plate to blade coating film forming.The micro-pore diameter of barrier film prepared by this embodiment of take is 100 μ m, and pick up is up to 400%.
Claims (7)
1. the PVDF-HFP micropore polymer diaphragm with grappling humidification, it is characterized in that: hygrometric state barrier film component contains polymer P VDF-HFP, ball cagelike silsesquioxane, slaine, organic solvent and non-solvent, wherein each constituent mass proportioning of hygrometric state barrier film is: 5.2～17.4 parts of polymer P VDF-HFP10～14.5 part, 0.5～4.3 part of ball cagelike silsesquioxane, 0.05～0.6 part of slaine, 52.0～110 parts of organic solvents and non-solvents.
2. the PVDF-HFP micropore polymer diaphragm with grappling humidification according to claim 1, it is characterized in that: the mass ratio of polymer P VDF-HFP and organic solvent is 0.13～0.19:1, the mass ratio of ball cagelike silsesquioxane and polymer P VDF-HFP is 0.01～0.30:1, the mass ratio of slaine and polymer P VDF-HFP is 0.005～0.05:1, and the mass ratio of non-solvent and organic solvent is 0.10～0.16:1; Micro-pore diameter is 20 μ m～100 μ m.
3. the PVDF-HFP micropore polymer diaphragm with grappling humidification according to claim 1, is characterized in that described slaine is a kind of in calgon, potassium chloride, potash or two kinds.
4. the PVDF-HFP micropore polymer diaphragm with grappling humidification according to claim 1, is characterized in that described organic solvent is acetone, DMF, one or both in 1-METHYLPYRROLIDONE.
5. the PVDF-HFP micropore polymer diaphragm with grappling humidification according to claim 1, is characterized in that described non-solvent is a kind of in water, absolute ethyl alcohol.
6. the preparation method with the PVDF-HFP micropore polymer diaphragm of grappling humidification, it is characterized in that concrete steps are as follows: (1) is dissolved in polymer P VDF-HFP in organic solvent, through heating, stirring, treat that it fully dissolves, add goal cagelike silsesquioxane, continue strong heating, heating reflux temperature is 50 ℃～100 ℃; Stir after 2～5h, obtain dispersed better colloid emulsion; (2) slaine and non-solvent are mixed, make mixed liquor standby; (3) mixed liquor obtaining in step (2) is dropwise added in the colloid emulsion being obtained by step (1), stir evenly; (4) adopt liquid the tape casting that the colloid mixed liquor in step (3) is cast on glass plate, blade coating film forming; Take off film, thickness is 18 μ m～45 μ m, at the temperature of 50 ℃～70 ℃, film is carried out to 1 h～2h vacuum drying; Porosity is 30%～70%.
7. the preparation method with the PVDF-HFP micropore polymer diaphragm of grappling humidification according to claim 5, is characterized in that described polymer P VDF-HFP weight average molecular weight is 400,000～500,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310524062.8A CN103545476B (en) | 2013-10-30 | 2013-10-30 | There is PVDF-HFP micropore polymer diaphragm and the preparation method of grappling humidification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310524062.8A CN103545476B (en) | 2013-10-30 | 2013-10-30 | There is PVDF-HFP micropore polymer diaphragm and the preparation method of grappling humidification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103545476A true CN103545476A (en) | 2014-01-29 |
| CN103545476B CN103545476B (en) | 2016-03-02 |
Family
ID=49968721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310524062.8A Active CN103545476B (en) | 2013-10-30 | 2013-10-30 | There is PVDF-HFP micropore polymer diaphragm and the preparation method of grappling humidification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103545476B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045851A (en) * | 2014-06-10 | 2014-09-17 | 中国第一汽车股份有限公司 | Preparation method of microporous polymer diaphragm with high mechanical strength and heat resistance |
| CN107768581A (en) * | 2017-10-27 | 2018-03-06 | 新乡市中科科技有限公司 | A kind of lithium battery POSS enhancing aramid fiber coating barrier films and preparation method thereof |
| CN108134034A (en) * | 2017-12-21 | 2018-06-08 | 深圳锂硫科技有限公司 | A kind of method that lithium battery diaphragm is prepared based on mixed solvent multistage Volatilization mechanism |
| CN110760225A (en) * | 2019-10-31 | 2020-02-07 | 深圳中科瑞能实业有限公司 | Production method of gel polymer electrolyte porous membrane |
| CN110854341A (en) * | 2019-11-15 | 2020-02-28 | 上海化工研究院有限公司 | Preparation method of high-performance lithium battery diaphragm |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247741A (en) * | 2000-03-08 | 2001-09-11 | Japan Automobile Research Inst Inc | Ion-conducting film and method of producing the same |
| JP2004002658A (en) * | 2001-12-28 | 2004-01-08 | Policell Technologies Inc | Thermally activated porous membrane and its application to storage battery |
| CN102731944A (en) * | 2012-06-21 | 2012-10-17 | 四川大学 | Copolymer-sylvite composite film material and its preparation method |
| CN102898573A (en) * | 2012-04-01 | 2013-01-30 | 浙江工业大学 | Siloxane-containing vinyl chloride copolymer, preparation method of the siloxane-containing vinyl chloride copolymer, battery division plate prepared from the siloxane-containing vinyl chloride copolymer, and manufacturing method of the battery division plate |
-
2013
- 2013-10-30 CN CN201310524062.8A patent/CN103545476B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247741A (en) * | 2000-03-08 | 2001-09-11 | Japan Automobile Research Inst Inc | Ion-conducting film and method of producing the same |
| JP2004002658A (en) * | 2001-12-28 | 2004-01-08 | Policell Technologies Inc | Thermally activated porous membrane and its application to storage battery |
| CN102898573A (en) * | 2012-04-01 | 2013-01-30 | 浙江工业大学 | Siloxane-containing vinyl chloride copolymer, preparation method of the siloxane-containing vinyl chloride copolymer, battery division plate prepared from the siloxane-containing vinyl chloride copolymer, and manufacturing method of the battery division plate |
| CN102731944A (en) * | 2012-06-21 | 2012-10-17 | 四川大学 | Copolymer-sylvite composite film material and its preparation method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045851A (en) * | 2014-06-10 | 2014-09-17 | 中国第一汽车股份有限公司 | Preparation method of microporous polymer diaphragm with high mechanical strength and heat resistance |
| CN107768581A (en) * | 2017-10-27 | 2018-03-06 | 新乡市中科科技有限公司 | A kind of lithium battery POSS enhancing aramid fiber coating barrier films and preparation method thereof |
| CN107768581B (en) * | 2017-10-27 | 2019-10-29 | 新乡市中科科技有限公司 | A kind of lithium battery POSS enhancing aramid fiber coating diaphragm and preparation method thereof |
| CN108134034A (en) * | 2017-12-21 | 2018-06-08 | 深圳锂硫科技有限公司 | A kind of method that lithium battery diaphragm is prepared based on mixed solvent multistage Volatilization mechanism |
| CN110760225A (en) * | 2019-10-31 | 2020-02-07 | 深圳中科瑞能实业有限公司 | Production method of gel polymer electrolyte porous membrane |
| CN110854341A (en) * | 2019-11-15 | 2020-02-28 | 上海化工研究院有限公司 | Preparation method of high-performance lithium battery diaphragm |
| CN110854341B (en) * | 2019-11-15 | 2022-11-08 | 上海化工研究院有限公司 | Preparation method of high-performance lithium battery diaphragm |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103545476B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109494390A (en) | A kind of modified solid electrolyte membrane and preparation method thereof and lithium battery | |
| CN103545476B (en) | There is PVDF-HFP micropore polymer diaphragm and the preparation method of grappling humidification | |
| CN105428571A (en) | PVDF-HFP based polymer membrane prepared from polydopamine modified ceramic particles and preparation method | |
| JP5616978B2 (en) | Method for producing a proton conducting membrane | |
| CN102044702B (en) | Composite polymer electrolyte for lithium ion battery and preparation method thereof | |
| CN105529496B (en) | Gel polymer electrolyte membrane and preparation method thereof | |
| CN102593403B (en) | Diaphragm for high thermal safety temperature lithium ion cell and preparation method thereof | |
| CN104362289A (en) | Lithium ion battery pole piece provided with inorganic isolating layers, battery comprising the pole piece and preparation method for pole piece | |
| CN101662042B (en) | Polymer lithium ion battery and preparation method of diaphragm thereof | |
| WO2021129583A1 (en) | Polymer electrolyte, and lithium ion battery comprising same | |
| CN106684360B (en) | Carbon coating method, negative electrode material and the lithium ion battery of artificial plumbago negative pole material | |
| CN104466063B (en) | Poly-dopamine surface modification polyether sulfone nanofiber composite diaphragm, preparation method and application | |
| CN101662041B (en) | Method for preparing gel polymer lithium ion battery | |
| Zheng et al. | Cellulose-reinforced poly (cyclocarbonate-ether)-based composite polymer electrolyte and facile gel interfacial modification for solid-state lithium-ion batteries | |
| CN105585732A (en) | Ultraviolet crosslinking polyaryletherketone porous membrane, preparation method and application of ultraviolet crosslinking polyaryletherketone porous membrane | |
| CN104051691A (en) | Preparation method of polydopamine-based modified composite polymer diaphragm | |
| CN108063208A (en) | A kind of high-performance lithium battery porous septum and preparation method thereof | |
| CN106848394A (en) | A kind of solid polymer electrolyte for adding modified graphene quantum dot and preparation method thereof | |
| CN102888014A (en) | Porous composite polymer electrolyte and its preparation method and use | |
| CN105390642A (en) | Preparation method for poly-dopamine modified ceramic particle nonwoven diaphragm | |
| CN103413906B (en) | A kind of high liquid-absorbing and oxidative resistance zinc-silver oxide cell barrier film and preparation method thereof | |
| CN109698384A (en) | A kind of preparation method of cylindrical mixing solid-liquid lithium ion battery | |
| CN101851412A (en) | High-safety polymer electrolyte as well as preparation method and application thereof | |
| CN109286038B (en) | Novel solid electrolyte and preparation method thereof | |
| CN103915650B (en) | A kind of lithium ion battery polymer dielectric and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |